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Title: Direct observation of the energetics at a semiconductor/liquid junction by operando X-ray photoelectron spectroscopy

Abstract

Photoelectrochemical (PEC) cells based on semiconductor/liquid interfaces offer an approach of converting solar energy to electricity or fuels. Currently, the understanding of semiconductor/liquid interfaces is inferred from experiments and models. Operando ambient-pressure X-ray photoelectron spectroscopy (AP-XPS) has been used herein to directly characterize the semiconductor/liquid junction at room temperature under real-time electrochemical control. X-ray synchrotron radiation in conjunction with AP-XPS has enabled simultaneous monitoring of the solid surface, the solid/electrolyte interface, and the bulk electrolyte of a PEC cell as a function of the applied potential, U. The observed shifts in binding energy with respect to the applied potential have directly revealed ohmic and rectifying junction behavior on metallized and semiconducting samples, respectively. Additionally, the non-linear response of the core level binding energies to changes in the applied electrode potential has revealed the influence of defect-derived electronic states on the Galvani potential across the complete cell.

Authors:
 [1];  [1];  [1];  [2];  [2];  [3];  [3];  [2];  [4];  [5];  [6];  [7];  [1]
+ Show Author Affiliations
  1. California Institute of Technology (CalTech), Pasadena, CA (United States). Joint Center for Artificial Photosynthesis (JCAP)
  2. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)
  3. California Institute of Technology (CalTech), Pasadena, CA (United States). Joint Center for Artificial Photosynthesis (JCAP); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)
  4. Technical Univ. of Darmstadt (Germany)
  5. California Institute of Technology (CalTech), Pasadena, CA (United States). Joint Center for Artificial Photosynthesis (JCAP) and Beckman Inst.
  6. California Institute of Technology (CalTech), Pasadena, CA (United States). Joint Center for Artificial Photosynthesis (JCAP) and Kavli Nanoscience Inst.
  7. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS); Chinese Academy of Sciences (CAS), Shanghai (China). Shanghai Inst. of Microsystem
Publication Date:
Research Org.:
California Institute of Technology (CalTech), Pasadena, CA (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1634114
Grant/Contract Number:  
SC0004993; AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Energy & Environmental Science
Additional Journal Information:
Journal Volume: 8; Journal Issue: 8; Journal ID: ISSN 1754-5692
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
30 DIRECT ENERGY CONVERSION

Citation Formats

Lichterman, Michael F., Hu, Shu, Richter, Matthias H., Crumlin, Ethan J., Axnanda, Stephanus, Favaro, Marco, Drisdell, Walter, Hussain, Zahid, Mayer, Thomas, Brunschwig, Bruce S., Lewis, Nathan S., Liu, Zhi, and Lewerenz, Hans-Joachim. Direct observation of the energetics at a semiconductor/liquid junction by operando X-ray photoelectron spectroscopy. United States: N. p., 2015. Web. doi:10.1039/C5EE01014D.
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Lichterman, Michael F., Hu, Shu, Richter, Matthias H., Crumlin, Ethan J., Axnanda, Stephanus, Favaro, Marco, Drisdell, Walter, Hussain, Zahid, Mayer, Thomas, Brunschwig, Bruce S., Lewis, Nathan S., Liu, Zhi, & Lewerenz, Hans-Joachim. Direct observation of the energetics at a semiconductor/liquid junction by operando X-ray photoelectron spectroscopy. United States. https://doi.org/10.1039/C5EE01014D
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Lichterman, Michael F., Hu, Shu, Richter, Matthias H., Crumlin, Ethan J., Axnanda, Stephanus, Favaro, Marco, Drisdell, Walter, Hussain, Zahid, Mayer, Thomas, Brunschwig, Bruce S., Lewis, Nathan S., Liu, Zhi, and Lewerenz, Hans-Joachim. Fri . "Direct observation of the energetics at a semiconductor/liquid junction by operando X-ray photoelectron spectroscopy". United States. https://doi.org/10.1039/C5EE01014D. https://www.osti.gov/servlets/purl/1634114.
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@article{osti_1634114,
title = {Direct observation of the energetics at a semiconductor/liquid junction by operando X-ray photoelectron spectroscopy},
author = {Lichterman, Michael F. and Hu, Shu and Richter, Matthias H. and Crumlin, Ethan J. and Axnanda, Stephanus and Favaro, Marco and Drisdell, Walter and Hussain, Zahid and Mayer, Thomas and Brunschwig, Bruce S. and Lewis, Nathan S. and Liu, Zhi and Lewerenz, Hans-Joachim},
abstractNote = {Photoelectrochemical (PEC) cells based on semiconductor/liquid interfaces offer an approach of converting solar energy to electricity or fuels. Currently, the understanding of semiconductor/liquid interfaces is inferred from experiments and models. Operando ambient-pressure X-ray photoelectron spectroscopy (AP-XPS) has been used herein to directly characterize the semiconductor/liquid junction at room temperature under real-time electrochemical control. X-ray synchrotron radiation in conjunction with AP-XPS has enabled simultaneous monitoring of the solid surface, the solid/electrolyte interface, and the bulk electrolyte of a PEC cell as a function of the applied potential, U. The observed shifts in binding energy with respect to the applied potential have directly revealed ohmic and rectifying junction behavior on metallized and semiconducting samples, respectively. Additionally, the non-linear response of the core level binding energies to changes in the applied electrode potential has revealed the influence of defect-derived electronic states on the Galvani potential across the complete cell.},
doi = {10.1039/C5EE01014D},
journal = {Energy & Environmental Science},
number = 8,
volume = 8,
place = {United States},
year = {Fri May 29 00:00:00 EDT 2015},
month = {Fri May 29 00:00:00 EDT 2015}
}
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Journal Article:
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Publisher's Version of Record
https://doi.org/10.1039/C5EE01014D
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Cited by: 123 works
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Figures / Tables:

Fig. 1 Fig. 1: (a) Scheme of the principal arrangement of p+-Si/TiO2/H2O(liq.)/ H2O(gas) to the analyzer front cone. (b) The energy band relations of the p+-Si/TiO2/H2O(liq.)/H2O(gas) system under applied potential U. The working electrode (Si) and analyzer are grounded and all the kinetic energies of the emitted photoelectrons are referenced to themore » Fermi energy of the analyzer. In the three-electrode configuration the Fermi energy is shifted by U with respect to the reference electrode. (c) The core level emission under applied potential (dashed curves) with respect to the core level emission under open circuit (solid line). The effective potential Ueff is given by eUeff(U) = eU + E$^0_{REF}$ - μ$^S_e$.« less
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